Water- and oil-repellent fluoroacrylates

ABSTRACT

Fluoroacrylates comprise the reaction product of: (a) at least one fluorochemical alcohol represented by the formula: 
 
C n F 2n+1 —X—OH 
wherein: 
 
n=1 to 4,  
                 
R=hydrogen or an alkyl group of 1 to 4 carbon atoms, m=2 to 8, 
             R f =C n F 2n+1 , y=0 to 6, and q=1 to 8; (b) at least one unbranched symmetric diusocyanate; and (c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoro acrylate monomer having 2 to about 30 carbon atoms in its alkylene portion.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. Ser. No. 11/027,604, filed Dec.28, 2004, now allowed, which claims priority to U.S. Provisional PatentApplication No. 60/534,203, filed Dec. 31, 2003, the disclosure of whichis incorporated by reference in its entirety herein.

FIELD

This invention relates to water- and oil-repellent fluoroacrylatemonomers and polymers.

BACKGROUND

Various fluorinated acrylic resins containing urethane linkages areknown to have oil and water repellency properties (see, for example,U.S. Pat. No. 4,321,404 (Williams et al.), U.S. Pat. No. 4,778,915 (Linaet al.), U.S. Pat. No. 4,920,190 (Lina et al.), U.S. Pat. No. 5,144,056(Anton et al.), and U.S. Pat. No. 5,446,118 (Shen et al.)). These resinscan be polymerized and applied as coatings to substrates such as, forexample, textiles, carpets, wall coverings, leather, and the like toimpart water- and oil repellency.

Typically, these resins comprise long chain pendant perfluorinatedgroups (for example, 8 carbon atoms or greater) because long chainsreadily align parallel to adjacent pendant groups attached to acrylicbackbone units, and thus maximize water- and oil-repellency. However,long chain perfluorinated group-containing compounds such as, forexample, perfluorooctyl containing compounds may bioaccumulate in livingorganisms (see, for example, U.S. Pat. No. 5,688,884 (Baker et al.)).

SUMMARY

In view of the foregoing, we recognize that there is a need forpolymerizable water- and oil-repellent acrylic resins that are lessbioaccumulative.

Briefly, in one aspect, the present invention provides water- andoil-repellent fluoroacrylates that have short chain perfluorinatedgroups (5 carbon atoms or less), which are believed to be less toxic andless bioaccumulative than longer chain perfluorinated groups (see, forexample, WO 01/30873). The fluoroacrylates of the invention comprise thereaction product of:

-   -   (a) at least one fluorochemical alcohol represented by the        formula:        C_(n)F_(2n+1)—X—OH    -   wherein:        -   n=1 to 5,        -   R=hydrogen or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F_(2n+1),        -   y=0 to 6, and        -   q=1 to 8;    -   (b) at least one unbranched symmetric dilsocyanate; and    -   (c) at least one hydroxy-terminated alkyl (meth)acrylate or        2-fluoroacrylate monomer having 2 to about 30 carbon atoms in        its alkylene portion.

As used herein, the term “(meth)acrylate monomer” refers to bothacrylate monomers and methacrylate monomers.

The invention also provides fluoroacrylates represented by the followinggeneral formula:C_(n)F_(2n+1)—X—OC(O)NH—A—HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂

-   -   wherein:        -   n=1 to 5,        -   R=H or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F_(2n+1),        -   y=0 to 6,        -   q=1 to 8,        -   A=an unbranched symmetric alkylene group, arylene group, or            aralkylene group,        -   p=2 to 30, and        -   R′=H, CH₃, or F.

It has been discovered that the fluoroacrylates of the invention exhibitgood water- and oil-repellency properties. In light of the prior art,one would expect that fluoroacrylates derived from shorterperfluorinated chains would not be as effective at imparting water- andoil-repellency as those derived from longer perfluorinated chains (see,for example, U.S. Pat. No. 2,803,615 (Ahlbrecht et al.) and U.S. Pat.No. 3,787,351 (Olson)). Surprisingly, however, the fluoroacrylates ofthe invention exhibit water- and oil-repellency comparable tofluoroacrylates with longer perfluorinated chains.

The fluoroacrylates of the invention therefore meet the need in the artfor polymerizable water- and oil-repellent acrylic resins that are lessbioaccumulative.

In another aspect, this invention provides fluorinated isocyanates thatare useful in making the fluoroacrylates of the invention. Thefluorinated isocyanates can be represented by the following generalformula:C_(n)F_(2n+1)—X—OC(O)NH—A—NCO

-   -   wherein:        -   n=1 to 5,        -   R=H or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F₂₊₁,        -   y=0 to 6,        -   q=1 to 8, and        -   A=an unbranched symmetric alkylene group, arylene group, or            aralkylene group.

In other aspects, this invention also provides fluorinated acrylicpolymers comprising repeating units of the fluoroacrylates of theinvention, coating compositions and release coating compositionscomprising the fluorinated acrylic polymers, and articles coated withthe coating or release coating compositions.

DETAILED DESCRIPTION

Fluorochemical alcohols that are useful in the fluoroacrylates of theinvention can be represented by the formula:C_(n)F_(2n+1)—X—OH

-   -   wherein:        -   n=1 to 5,        -   R=hydrogen or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F_(2n+1),        -   y=0 to 6, and        -   q=1 to 8.

Representative examples of suitable alcohols include CF₃CH₂OH,(CF₃)₂CHOH, (CF₃)₂CFCH₂OH, C₂F₅SO₂NH(CH₂)₂OH, C₂F₅SO₂NCH₃(CH₂)₂OH,C₂F₅SO₂NCH₃(CH₂)₄OH, C₂F₅SO₂NC₂H₅(CH₂)₆OH, C₂F₅(CH₂)₄OH,C₂F₅CONH(CH₂)₄OH, C₃F₇SO₂NCH₃(CH₂)₃OH, C₃F₇SO₂NH(CH₂)₂OH, C₃F₇CH₂OH,C₃F₇CONH(CH₂)₈OH, C₄F₉(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉CONH(CH₂)₂OH,C₄F₉SO₂NCH₃(CH₂)₄OH, C₄F₉SO₂NH(CH₂)₇OH, C₄F₉SO₂NC₃H₇(CH₂)₂OH,C₄F₉SO₂NC₄H₉(CH₂)₂OH, C₅F₁₁SO₂NCH₃(CH₂)₂OH, C₅F₁₁CONH(CH₂)₂OH, andC₅F₁₁(CH₂)₄OH.

Preferably, n is 1 to 4; more preferably, n is 4. Preferably, m is 2 to4. Preferably, q is 2.

Preferably, X is

More preferably, X is

Most preferably, X is selected from the group consisting of

Preferred fluorochemical alcohols include, for example,C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, and C₄F₉(CH₂)₂OH. A morepreferred fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

Symmetric diisocyanates are diisocyanates that meet the three elementsof symmetry as defined by Hawley's Condensed Chemical Dictionary 1067(1997). First, they have a center of symmetry, around which theconstituent atoms are located in an ordered arrangement. There is onlyone such center in the molecule, which may or may not be an atom.Second, they have a plane of symmetry, which divides the molecule intomirror-image segments. Third, they have axes of symmetry, which can berepresented by lines passing through the center of symmetry. If themolecule is rotated, it will have the same position in space more thanonce in a complete 360° turn.

As used herein, the term “unbranched” means that the symmetricdiisocyanate does not contain any subordinate chains of one or morecarbon atoms.

Representative examples of unbranched symmetric diisocyanates include4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate(HDI), 1,4-phenylene diisocyanate (PDI), 1,4-butane diisocyanate (BDI),1,8-octane diisocyanate (ODI), 1,12-dodecane diisocyanate, and1,4-xylylene diisocyanate (XDI).

Preferred unbranched symmetric diusocyanates include, for example, MDI,HDI, and PDI. A more preferred unbranched symmetric diisocyanate is MDI.In its pure form, MDI is commercially available as Isonate™ 125M fromDow Chemical Company (Midland, Mich.), and as Mondur™ from BayerPolymers (Pittsburgh, Pa.).

Hydroxy-terminated alkyl (meth)acrylate and 2-fluoroacrylate monomersthat are useful in the fluoroacrylates of the invention can have from 2to about 30 carbon atoms (preferably, from 2 to about 12 carbon atoms)in their alkylene portion.

Preferably, the hydroxy-terminated alkyl (meth)acrylate monomer is ahydroxy-terminated alkyl acrylate. Preferred hydroxy-terminated alkylacrylates include, for example, hydroxy ethyl acrylate, hydroxy butylacrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxydodecyl acrylate, and mixtures thereof.

The fluoroacrylates of the invention can be prepared, for example, byfirst combining the fluorochemical alcohol and the unbranched symmetricdiisocyanate in a solvent, and then adding the hydroxy-terminated alkyl(meth)acrylate. Useful solvents include esters (for example, ethylacetate), ketones (for example, methyl ethyl ketone), ethers (forexample, methyl-tert-butyl ether), and aromatic solvents (for example,toluene).

Preferably, the reaction mixture is agitated. The reaction can generallybe carried out at a temperature between room temperature and about 120°C. (preferably, between about 50° C. and about 70° C.).

Typically the reaction is carried out in the presence of a catalyst.Useful catalysts include bases (for example, tertiary amines, alkoxides,and carboxylates), metal salts and chelates, organometallic compounds,acids and urethanes. Preferably, the catalyst is an organotin compound(for example, dibutyltin dilaurate (DBTDL) or a tertiary amine (forexample, diazobicyclo[2.2.2]octane (DABCO)), or a combination thereof.More preferably, the catalyst is DBTDL.

When fluorochemical alcohols represented by the formulaC_(n)F_(2n+1)SO₂NCH₃(CH₂)_(m)OH, wherein n=2 to 5, and m=2 to 4, arereacted with MDI, the process described in U.S. patent application Ser.No. 10/751142, entitled “Process For Preparing FluorochemicalMonoisocyanates,” filed on Dec. 31, 2003, can be used.

Fluoroacrylates of the invention can be represented by the followinggeneral formula:C_(n)F_(2n+1)—X—OC(O)NH—A—HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂

-   -   wherein:        -   n=1 to 5,        -   R=H or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F_(2n+1),        -   y=0 to 6,        -   q=1 to 8,        -   A=an unbranched symmetric alkylene group, arylene group, or            aralkylene group,        -   p=2 to 30, and        -   R′=H, CH₃, or F.

Preferably, n is 1 to 4; more preferably, n is 4. Preferably, q is 2.

Preferably, X is

and m is 2 to 4.

Preferably, A is selected from the group consisting of —C₆H₁₂—,

more preferably, A is

Preferably, p is 2 to 12; more preferably, p is selected from the groupconsisting of 2, 4, 6, 10, and 12; most preferably, p is 2.

Preferably, R′ is H.

Fluoroacrylates of the invention can be polymerized to yield afluorinated acrylic polymer. Fluorinated acrylic polymers comprisingrepeating units of fluoroacrylates of the invention exhibit water- andoil-repellency properties.

Fluoroacrylates of the invention can also be copolymerized with one ormore nonfunctional comonomers and/or functional comonomers.

Nonfunctional comonomers such as, for example, alkyl acrylates canimprove durability and film-forming properties. Representative examplesof useful nonfunctional comonomers include methyl (meth)acrylate, butylacrylate, isobutyl (meth)acrylate, hexyl acrylate, dodecyl acrylate, andoctadecyl acrylate. Nonfunctional comonomers can typically becopolymerized with the fluoroacrylates of the invention in about up to a1:1 molar ratio.

Functional comonomers can provide properties such as, for example,adhesion, hydrophilicity, reactivity, or low glass transitiontemperatures. Groups that are useful in functional comonomers include,for example, hydroxy, carboxy, quaternary ammonium, acetate,pyrrolidine, polyethylene glycol, sulfonic acid, trialkoxysilane, andsilicone. These groups can generally be introduced into the polymer atless than about 20 weight percent (preferably, less than about 5 weightpercent). Useful functional comonomers include, for example, acrylicacid, methacrylic acid, N-vinyl 2-pyrrolidinone, and hydroxypropylacrylate.

Fluoroacrylates of the invention can also be polymerized withmethacrylate functional polydimethyl siloxanes such as, for example,methacryloxy propyl polydimethyl silicone, to prepare fluorinatedacrylic/siloxane graft copolymers.

Fluorinated acrylic polymers of the invention can be used in coatingcompositions to impart water- and oil-repellency to a wide variety ofsubstrates. The coating compositions comprise a fluorinated acrylicpolymer of the invention and a solvent (for example, water and/or anorganic solvent). When the solvent is water, the coating compositiontypically further comprises a surfactant.

The fluorinated acrylic polymers of the invention can be dissolved,suspended, or dispersed in a wide variety of solvents to form coatingcompositions suitable for coating onto a substrate. The coatingcompositions can generally contain from about 0.1 about 10 percentfluorinated acrylic polymer (preferably about 1 to about 5 percent),based on the weight of the coating composition.

The coating compositions can be applied to a wide variety of substratessuch as, for example, fibrous substrates and hard substrates. Fibroussubstrates include, for example, woven, knit, and nonwoven fabrics,textiles, carpets, leather, and paper. Hard substrates include, forexample, glass, ceramic, masonry, concrete, natural stone, man-madestone, grout, metals, wood, plastics, and painted surfaces.

The coating compositions can be applied to a substrate (or articlescomprising a substrate) by standard methods such as, for example,spraying, padding, dipping, roll coating, brushing, or exhaustion.Optionally, the composition can be dried to remove any remaining wateror solvent.

Polymers and copolymers of the invention can be used for releasecoatings. Comonomers that are useful in release coatings include, forexample, octadecyl acrylate, N-vinyl 2-pyrrolidinone, methacryloxypropyl dimethyl siloxane, acrylic acid, methacrylic acid, acrylonitrileand methyl acrylate. The release coating compositions may or may notrequire a curing step after coating on a substrate.

Coating compositions useful for release coatings can be applied tosurfaces requiring release properties from adhesives. Substratessuitable for release coatings include, for example, paper, metal sheets,foils, non-woven fabrics, and films of thermoplastic resins such aspolyesters, polyamides, polyolefins, polycarbonates, and polyvinylchloride.

Release coating compositions can be applied to suitable substrates byconventional coating techniques such as, for example, wire-wound rod,direct gravure, offset gravure, reverse roll, air-knife, and trailingblade coating. The resulting release coating compositions can provideeffective release for a wide variety of pressure sensitive adhesivessuch as, for example, natural rubber based adhesives, silicone basedadhesives, acrylic adhesives, and other synthetic film-formingelastomeric adhesives.

EXAMPLES

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. Desig- Name,Formula and/or nator Structure Availability A-174CH₂═C(CH₃)CO₂C₃H₆Si(OMe)₃ Sigma Aldrich, Milwaukee, WI AA Acrylic acid;Sigma HOC(O)CH═CH₂ Aldrich BA Butyl acrylate; Sigma C₄H₉OC(O) CH═CH₂Aldrich DBTDL Dibutyltin dilaurate Sigma Aldrich DDA Dodecyl acrylate;Sigma CH₃(CH₂)₁₁OC(O)CH═CH₂ Aldrich DDSH Dodecylthiol; CH₃(CH₂)₁₁SHSigma Aldrich DMF Dimethyl formamide Sigma Aldrich HDI 1,6-Hexanediisocyanate Sigma OCN(CH₂)₆NCO Aldrich HEA Hydroxyethyl acrylate; SigmaHOCH₂CH₂OC(O)CH═CH₂ Aldrich HEMA Hydroxyethyl Sigma methacrylate;Aldrich HOCH₂CH₂OC(O)C(CH₃)═CH₂ HOBA Hydroxybutyl acrylate; Nippon KaseiHO(CH₂)₄OC(O)CH═CH₂ Chemical Co., Tokyo. HOPA Hydroxypropyl acrylate;Sigma isomer mixture; Aldrich HOCH(CH₃)CH₂OC(O)CH═CH₂ andHOCH₂CH(CH₃)OCOCH═CH₂ H12- MDI

Bayer Polymers LLC, Pittsburgh, PA IOA Isooctyl acrylate; 3M, St Paul,i-C₈H₇OC(O)CH═CH₂ MN IPDI

Sigma- Aldrich MA Methyl acrylate; Sigma- CH₃OC(O)CH═CH₂ Aldrich MAAMethacrylic acid; Sigma- HOC(O)C CH₃═CH₂ Aldrich MDI

Sigma- Aldrich MEK Methyl ethyl ketone; Sigma- CH₃C(O)C₂H₅ Aldrich ODAOctadecyl acrylate; Sigma- CH₃(CH₂)₁₇OC(O)CH═CH₂ Aldrich PDI

Sigma- Aldrich Pheno- thiazine

Sigma- Aldrich TDI

Sigma- Aldrich TMXDI

American Cyanamid ″VAZO NCC(Me) (Et)N═NC(Me) (Et)CN DuPont, 67″Wilmington, DE

Preparation of HOHA (6-Hydroxyhexyl Acrylate)

118 g (1 mol; available from Sigma-Aldrich) 1,6-hexanediol, 36 g (0.5mol; available from Sigma-Aldrich) AA, 1.0 g p-toluenesulfonic acidhydrate (available from Sigma-Aldrich), 0.016 g phenothiazine, 0.055 ghydroquinone monomethyl ether (available from Sigma-Aldrich) and 300 mlheptane was stirred at reflux in a 3 necked 1-L round bottom flaskequipped with a modified Dean-Stark trap. After 5 hr at reflux, 8.4 ml(0.47 mol) water had collected. Upon cooling, two layers formed. The toplayer contained hexanediol diacrylate and heptane. The bottom layer(141.2 g) was analyzed by gas liquid chromatography (GLC) afterderivatization with TFAA (trifluoroacetic anhydride available fromAldrich) as 13.9% unreacted diol, 11.0% desired monoacrylate, and atrace of diacrylate. The lower layer was dissolved in 100 ml ethylacetate and washed three times with 100 ml of water, stripped to 55.7 g,15% diol, 84% monoacrylate (HOHA), and 1% diacrylate. To the aboveprepared HOHA mixture (19 g), 100 ml ethyl acetate was added and thissolution was washed three times with 150 ml water. The last wash gave anemulsion, which was frozen and thawed to give two phases. The organicphase yielded HOHA (50.1 g red liquid; 99% pure).

Preparation of HOHMA (HO(CH₂)₆OC(O)C(CH₃)═CH₂)

HOHMA was prepared essentially according to the procedure described forHOHA with the exception that an equimolar amount of MAA is substitutedfor AA.

Preparation of HODDA (12-Hydroxydodecylacrylate)

In a similar fashion to the preparation of HOHA, 203 g (1.0 mol)dodecane-1,12-diol, 36.0 g (0.50 mol), 1.0 g AA, 0.018 g phenothiazine,0.034 hydroquinone monomethyl ether, and 350 ml heptane were heated atreflux 3.5 hr, and then allowed to cool and form a slurry. Filtrationyielded 147.0 g solid (96% diol by GLC analysis). The filtrant wasstripped to 120 g of an oil, 2% diol, 80% monoacrylate, and 18%diacrylate. Flash chromatography of 29.5 g from hexane-ethyl acetate85-15 (vol %) on 257 g 280-400 mesh silica gel (available fromSigma-Aldrich) yielded pure HODDA (17.1 g).

Preparation of C₄F₉SO₂NH(CH₃)

C₄F₉SO₂NH(CH₃) was prepared by essentially following the proceduredescribed in U.S. Pat. No. 6,664,354 (Savu et al.), Example 1, Part A.

Preparation of MeFBSE: C₄F₉SO₂N(CH₃)CH₂CH₂OH

MeFBSE was prepared by essentially following the procedure described inU.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A.

Preparation of MeFESE: C₂F₅SO₂N(CH₃)CH₂CH₂OH

MeFESE was prepared by essentially following the procedure described inU.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A with theexception that C₂F₅SO₂F (prepared essentially as described in U.S. Pat.No. 5,723,630) was used as a starting material.

Preparation of MeFBSEA: C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂

MeFBSEA was prepared by essentially following the procedure described inU.S. Pat. No. 6,664,354 (Savu et al.) Example 2, Part A & B.

Preparation of MeFESEA: C₂F₅SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂

A round bottom flask charged with 16.0 g (0.0623 mol)C₂F₅SO₂N(CH₃)(CH₂)₂OH, 33.8 g ethyl acetate, and 10.47 g (0.0810 mol)diisopropylethyl amine was placed in an ice bath and cooled to 7 C. Thereaction was fitted with a pressure equalizing addition funnel undernitrogen containing 7.33 g (0.0810 mol) acryloyl chloride which wasadded to the reaction over 12 min. At 200 min, 16.9 g more ethyl acetatewas added to the reaction, which was sequentially washed with 30 g 2%aqueous hydrochloric acid and 5% aqueous sodium bicarbonate, dried overanhydrous magnesium sulfate, filtered and concentrated on a rotaryevaporator at 55° C. under aspirator pressure to provide 11.93 g crudeproduct. A 7 cm diameter chromatographic column was filled with 230 g ofsilica gel (#SX1043U-3, grade 62, 60-200 mesh, from EM Science,Darmstadt, Germany) slurried with 60:40 by volume heptane:ethyl acetateand 11.93 g of the product was chromatographed using the column toprovide after concentration 7.06 g desired product.

Preparation of C8F₁₇SO₂NMeC₂H₄OC(O)CH═CH₂ (MeFOSEA)

MeFOSEA was prepared essentially as described in U.S. Pat. No. 6,664,354(Savu et al.) example 1A and example 2A and 2B with the exception thatC₈F₁₇SO₂F (available from Sigma-Aldrich) was used instead of C₄F₉SO₂F.

Preparation of C₄F₉(CH₂)₂OC(O)CH═CH₂

In a manner similar to the preparation ofC₂F₅SO₂N(CH₃)(CH₂)₂OC(O)CH═CH₂, 11.02 g (0.0417 mol) C₄F(CH₂)₂OH(available from TCI America, Portland Oreg.) and 7.01 g (0.0542 mol)diisopropylethyl amine in 22.94 g diethyl ether was reacted with 4.91 g(0.0542 mol) acryloyl chloride over 2 h, washed sequentially washed with30 g 2% aqueous hydrochloric acid and 5% aqueous sodium bicarbonate,dried over anhydrous magnesium sulfate, filtered and concentrated on arotary evaporator in a room temperature bath at aspirator pressure toprovide a crude product. This was combined with a similar preparation ofC₄F₉(CH₂)₂OC(O)CH═CH₂ made using the same ratios of starting materials,starting with 8.0 g C₄F₉(CH₂)₂OH to provide about 25 g of crude product.To these combined products was added 0.005 g p-methoxy phenol and 0.0013g phenothiazine, and the material was distilled under aspirator pressureat a head temperature of 67 C to provide 8.88 g of the desired product.

Preparation of EOSH: (CH₃(OCH₂CH₂)OC(O)CH₂SH)

A 500 mL three-necked round bottom flask was charged with 25.96 g ofCH₃(OCH₂CH₂)_(n)OH (MW=550; 47.20 mmol; available from Sigma-Aldrich),4.35 g HSCH₂CO₂H (47.28 mmol; available from Sigma-Aldrich), 2 drops ofCF₃SO₃H catalyst, and 120 mL toluene. The mixture was heated to refluxunder nitrogen at 115-120° C. with a mechanical stirrer for 8 hours.Water was removed by azeotropic distillation. Fourier Transform InfraredSpectroscopy (FTIR) analysis indicated the formation of EOSH. Thesolvent was stripped using a rotary evaporator (27.60 g).

Preparation of C₄F₉SO₂N(CH₃)C₂H₄OC(O)NHC₆H₄CH₂C₆H₄NCO (MeFBSE-MDI)

A one liter, three-necked round bottom flask, fitted with a heater,nitrogen inlet, reflux condenser and thermocouple was charged withMeFBSE (357.0 g; 1.0 mole) and MEK (600 mL) and heated to reflux, whiledistilling out 30 mL of MEK. The mixture was then cooled to 30° C. andtreated with MDI (750 g; 3.0 mole). The temperature of the mixture wasthen increased to about 40° C. for 4 hours, filtered and added totoluene (4 l). The resulting off white precipitate was collected byfiltration, and re-crystallized from toluene (white solid; 689.4 g; 57%yield). Structure was confirmed using liquid chromatography/massspectroscopy (LC/MS) and LC/UV analysis.

Preparation of C₄F₉SO₂N(CH₃)C₂H₄OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(MeFBSE-MDI-HEA)

A one L flask containing 500 mL ethyl acetate was heated to reflux underN₂, and 100 mL of ethyl acetate was distilled out. The remaining solventwas cooled under dry air and treated with 151.9 g MeFBSE-MDI, 29.1 g2-hydroxyethyl acrylate, 2 drops DBTDL, and 7 mg phenothiazine. After 5hr at 50° C., infrared spectroscopy indicated complete conversion of theisocyanate. The cloudy solution was filtered through 40 g diatomaceousearth and rinsed with hot ethyl acetate to give 473.5 g clear solution,(29.6% solids, yield as MeFBSE-MDI-HEA, 77%).

Preparation of C₂F₅SO₂N(CH₃)CH₂CH₂OC(O)NHC₆H₄CH₂C₆H₄NCO (MeFESE-MDI)

To a flask containing 37.5 g (0.15 mol) MDI in 75 g heptane that wasfiltered at 50° C. through a C porosity frit, to which was added twodrops of DBTDL at 50C was added 25.7 g (0.10 mol) C₂F₅SO₂N(CH₃)CH₂CH₂OHdropwise over 58 min. At 3.5 h, the resulting solid was filtered, rinsedwith 120 g heptane, and vacuumed dry under nitrogen to provide 69.43 gof a white powder that was 71% solids, the remainder being heptane.(49.29 g yield, 97.2%)

Preparation ofC₂F₅SO₂N(CH₃)CH₂CH₂OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(MeFESE-MDI-HEA)

A 250 mL round bottom equipped with overhead stirrer was charged with 40g of MeFESE-MDI (71% solids, 0.056 mol), 100 g ethyl acetate, 2 drops ofdibutylin dilaurate and heated to 50 C in a heating bath under nitrogen.Then 6.50 g (0.056 mol) hydroxyethylacrylate was added in one portion,followed by 6.3 mg of p-methoxy phenol. The bath temperature wasadjusted to 60° C. and the reaction ran for 14 h. The reaction wasallowed to cool to room temperature over two days, and an absence of theisocyanate peak at 2281 cm-1 was noted by FTIR. Phenothiazine (2 mg) wasadded to the reaction mixture which was then concentrated in a 55° C.bath at aspirator pressure to yield 35.3 g of a white solid.

The product was dissolved in 10 g ethyl acetate, and chromatographed ona 7 cm diameter chromatographic column filled with 230 g of silica gel(#SX1043U-3, grade 62, 60-200 mesh, from EM Science, Darmstadt, Germany)slurried with 50:50 by volume heptane:ethyl acetate to yield 20.13 g ofproduct.

Preparation of C₄F₉(CH₂)₂OC(O)NHC₆H₄CH₂C₆H₄NCO(C₄F(CH₂) ₂OH-MDI)

C₄F₉(CH₂)₂OH-MDI was prepared in a manner similar to the preparation ofMeFESE-MDI except that 17.7 g (0.071 moles) of MDI in 30 g of heptanewas reacted with 12.5 g (0.047 moles) of C₄F₉(CH₂)₂OH.

Preparation of C₄F₉(CH₂)₂OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(C₄F₉(CH₂)₂OH-MDI-HEA)

C₄F₉(CH₂)₂OH-MDI-HEA was prepared in a manner similar to the preparationof MeFESE-MDI-HEA except that 12.0 g (0.023 mole) of C₄F₉(CH₂)₂OH-MDIwas reacted with 2.71 g (0.023 mole) of hydroxyethyl acrylate in 40 g ofethyl acetate with DBTDL, followed by workup and chromatography toprovide 5.8 g of product.

Preparation ofCF₃CH₂OC(O)NHC₆H₄CH₂C₆H₄NCOOCH₂CH₂OC(O)CH═CH₂(CF₃CH₂OH-MDI-HEA)

A mixture of 33.0 g CF₃CH₂OH (available from Aldrich), 125 g MDI, 2drops DBTDL and 400 g heptane was stirred at 50° C. 20hr, filtered whilestill hot, and the collected solid recrystallized from toluene to give100 g of CF₃CH₂OH-MDI adduct. A solution of 7.0 g of the adduct, 2.32 gHEA, 1 drop DBTDL, and 30 mL dry THF was heated under N₂ for 20 hr atabout 60° C. Acetone (40 mL) was added to the resultant white slurry, asmall amount of insoluble material was filtered and the solution wasstripped to 7.6 g white solid. Flash chromatography with 80/20Hexane/ethyl acetate (v/v) on 200 g silica gel (280-400 mesh, Aldrich)gave 4.1 g pure monomer.

Preparation of poly-MeFBSE-MDI-HEA

A 125 ml bottle was charged with 6.0 g MeFBSE-MDI-HEA, 70 mg “VAZO 67”,and 24 g ethyl acetate. After purging with nitrogen for 35 seconds, thebottle was kept in a rotating water bath at 60° C. for 15 hr. Theresulting slurry was treated with about 50 ml methanol, filtered and thesolid was dispersed in 43 g ethyl acetate. On heating, the soliddissolved, and upon cooling, some solid precipitated. Addition of 6.0 gDMF gave complete solution.

General Procedure for Examples and Comparative Examples Listed in Table1 & 2.

For each example and comparative example, a 125 ml bottle was chargedwith 3.0-6.0 g of the fluoroacrylate listed in the table (preparedessentially as described above for MeFBSE-MDI-HEA), 15-40 mg “VAZO 67”,and sufficient ethyl acetate to yield a 25-30% by weight concentrationof monomer. Appropriate amounts of co-monomers were added to arrive atthe wt % listed in Table 2. After purging with nitrogen for 35-60seconds, the bottle was kept in a rotating water bath at 60° C. for24-48 hrs. The product often precipitated upon cooling. In some casesthe resulting polymer solution was poured into 300-400 mL of methanol.The precipitated polymer was subsequently dispersed in ethyl acetate toyield a 20-30 wt. % solution of polymer. On heating, the solid dissolvedand upon cooling, some solid usually precipitated. Addition of smallamounts of DMF gave complete solution.

Dynamic Contact Angle Measurement

A test solution, emulsion, or suspension (typically at about 3% solids)was applied to nylon 66 film (available from DuPont) by dip-coatingstrips of the film. Prior to coating the film was cleaned with methylalcohol. Using a small binder clip to hold one end of the nylon film,the strip was immersed in the treating solution, and then withdrawnslowly and smoothly from the solution. The coated strip was allowed toair dry in a protected location for a minimum of 30 minutes and then wascured for 10 minutes at 150° C.

Advancing and receding contact angles on the coated were measured usinga CAHN Dynamic Contact Angle Analyzer, Model DCA 322 (a Wilhelmy balanceapparatus equipped with a computer for control and data processing,commercially available from ATI, Madison, Wis.). Water and hexadecanewere used as probe liquids. Values for both water and hexadecane arereported.

Larger values of contact angles are indicative of better repellency.TABLE 1 Examples 1-16 and Comparative Examples C1-C11 Contact Angle indegrees Fluoroacrylate Advancing (Receding) Ex. Composition WaterHexadecane  1 MeFBSE-HDI-HOHA 124(93) 82(68)  2 MeFBSE-HDI-HODDA 125(100) 79(65)  3 MeFBSE-MDI-HEA  132(101) 91(55)  4 MeFBSE-MDI-HEMA123(87) 81(64)  5 MeFBSE-MDI-HOPA 121(86) 72(63)  6 MeFBSE-MDI-HOBA121(94) 79(69)  7 MeFBSE-MDI-HOHA  129(106) 83(70)  8 MeFBSE-MDI-HOHMA122(79) 72(65) C1 MeFBSE-IPDI-HEA 111(67) 66(35) C2 MeFBSE-IPDI-HEMA112(69) 65(32) C3 MeFBSE-IPDI-HOHA 113(65) 69(33) C4 MeFBSE-H12MDI-HOHA116(63) 62(37) C5 MeFBSE-TDI-HEA 117(80) 69(61) C6 MeFBSE-TDI-HEMA115(79) 67(58) C7 MeFBSE-TDI-HOHA 121(58) 71(56) C8 MeFBSE-TDI-HODDA106(67) 42(26)  9 MeFBSE-PDI-HEA  120(100) 98(55) 10 MeFBSE-PDI-HEMA120(92) 73(61) 11 MeFBSE-PDI-HOBA 120(94) 83(62) 12 MeFBSE-PDI-HOHA120(97) 82(67) 13 MeFBSE-PDI-HODDA  138(101) 86(56) C9 MeFBSE-TMXDI-HEA111(55) 60(39) 14 C₄F₉(CH₂)₂OH-MDI-HEA 125(86) 75(66) C10 C₄F₉(CH₂)₂OC(O)CH═CH₂ 127(51) 83(39) 15 MeFESE-MDI-HEA 117(79) 68(59)C11  MeFESEA 112(67) 62(43) 16 CF₃CH₂OH-MDI-HEA 121(70) 72(45)

TABLE 2 Examples 17-37 and Comparative Example C12 Contact Angle indegrees Fluoroacrylate/Comonomer Advancing (Receding) Ex. Composition(wt %) Water Hexadecane 17 MeFBSE-HDI-HOHA (80) 123(90) 81(63) DDA (20)18 MeFBSE-MDI-HEA (95)  128(111) 81(69) MA (5) 19 MeFBSE-MDI-HEA (89.4) 125(105) 79(72) MA (10.6) 20 MeFBSE-MDI-HEA (79.4) 120(81) 76(69) MA(21.6) 21 MeFBSE-MDI-HEA (90)  125(105) 80(69) BA (10) 22 MeFBSE-MDI-HEA(80) 120(97) 78(68) BA (20) 23 MeFBSE-MDI-HEA (90)  124(101) 81(70) IOA(10) 24 MeFBSE-MDI-HEA (80)  125(100) 79(63) IOA (20) 25 MeFBSE-MDI-HEA(70) 122(92) 79(64) IOA (30) 26 MeFBSE-MDI-HEA (80) 123(95) 78(67) ODA(20) 27 MeFBSE-MDI-HEA (70) 128(92) 81(66) ODA (30) 28 MeFBSE-MDI-HEA(60) 127(91) 80(68) ODA (40) 29 MeFBSE-MDI-HEA (50)  124(101) 78(72) ODA(50) 30 MeFBSE-MDI-HEA (75) 119(91) 77(66) MeFBSEA (25) 31MeFBSE-MDI-HOBA (75)  93(79) 82(70) DDA (25) 32 MeFBSE-MDI-HODDA (75)123(95) 82(40) DDA (25) C12   MeFBSE-TDI-HODDA (75) 118(68) 71(24) DDA(25) 33 MeFBSE-PDI-HEA (80) 116(85) 80(70) ODA (20) 34 MeFBSE-PDI-HOBA(80) 107(79) 80(68) ODA (20) 35 MeFBSE-PDI-HOHA (80) 108(80) 82(67) ODA(20) 36 MeFBSE-PDI-HODDA (80) 108(88) 80(69) ODA (20) 37 MeFESE-MDI-HEA(70)  119(109) 47(37) ODA (30)

Example 38 Preparation of MeFBSE-MDI-HEA/ODA/AA; 70/26/4

A 125 mL bottle with a magnetic stirrer was charged with 9.46 g 37%MeFBSE-MDI-HEA solution in ethyl acetate (3.50 g solid; 4.84 mmol), 1.30g ODA (4.005 mmol), 0.2 g AA (2.78 mmol), 28.55 g ethyl acetate and0.050 g “VAZO-67”. The solution was bubbled with nitrogen for twominutes. The sealed bottle was put in a 70° C. oil bath and stirred for24 hours.

Example 39 Preparation of MeFBSE-MDI-HEA/ODA/A-174 in ratio of 70/26/4

In a 125 mL bottle with a magnetic stirrer was charged with 9.46 g 37%MeFBSE-MDI-HEA solution in ethyl acetate (3.50 g solid, 4.84 mmol), 1.30g ODA (4.005 mmol), 0.2 g A-174 (0.805 mmol), 26.84 g ethyl acetate and0.050 g “VAZO-67”. The solution was bubbled with nitrogen for twominutes. The sealed bottle was put in a 70° C. oil bath and stirred for24 hours. TABLE 3 Examples 38-39 Contact Angle in degreesFluoroacrylate/Comonomer Advancing (Receding) Ex. Composition (wt %)Water Hexadecane 38 MeFBSE-MDI-HEA (70) 125(87) 80(67) ODA (26) AA (4)39 MeFBSE-MDI-HEA (70) 119(95) 81(67) ODA (26) A-174 (4)

Example 40 Preparation of MeFBSE-MDI-HEA/EOSH; 3.0/1.0

A 125 mL bottle with a magnetic stirrer was charged with 5.00 gMeFBSE-MDI-HEA (6.920 mmol), 0.52 g EOSH (2.308 mmol), 26.92 g ethylacetate and 0.064 g “VAZO-67”. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath withmagnetic stirring for 24 hours. The resulting solution showedprecipitation at room temperature. Addition of 5.0 g DMF gave a clearsolution.

Example 41 Preparation of MeFBSE-MDI-HEA/EOSH; 6.0/1.0

A 125 mL bottle with a magnetic stirrer was charged with 5.01 gMeFBSE-MDI-HEA (6.934 mmol), 0.72 g EOSH (1.154 mmol), 26.96 g ethylacetate and 0.055 g “VAZO-67”. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath withmagnetic stirring for 24 hours. The resulting solution showedprecipitation at room temperature. Addition of 5.0 g DMF gave a clearsolution.

Example 42 Preparation of MeFBSE-MDI-HEA/EOSH; 8.3/1

A 125 mL bottle with a magnetic stirrer was charged with 5.01 gMeFBSE-MDI-HEA (6.925 mmol), 0.52 g EOSH (0.833 mmol), 26.60 g ethylacetate and 0.054 g “VAZO-67”. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath withmagnetic stirring for 24 hours. The resulting solution showedprecipitation at room temperature. Addition of 5.0 g DMF gave a clearsolution.

Example 43 Preparation of H(MeFBSE-MDI-HEA)₄-SC₁₂H₂₅

A 125 mL bottle with a magnetic stirrer was charged with 4.99 gMeFBSE-MDI-HEA (6.9078 mmol), 0.35 g DDSH (1.729 mmol), 11.94 g ethylacetate and 0.055 g “VAZO-67”. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath andpolymerized with a magnetic stirring for 24 hours. The resultingsolution had precipitated white solid. Addition of 5 g DMF gave a clearsolution.

Example 44 Preparation of H(MeFBSE-MDI-HEA)₈-SC₁₂H₂₅

In a 125 mL bottle with a magnetic stirrer was charged with 5.02 gMeFBSE-MDI-HEA (6.940 mmol), 0.17 g DDSH (0.840 mmol), 12.0 g ethylacetate and 0.050 g “VAZO-67”. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath andpolymerized with a magnetic stirring for 24 hours. The resultingsolution had precipitated white solid. Addition of 5 g DMF turned thesolution clear (22.2% solid). TABLE 4 Examples 40-44 Contact Angle indegrees Fluoroacrylate/Comonomer Advancing (Receding) Ex. Composition(molar ratio) Water Hexadecane 40 MeFBSE-MDI-HEA (3.0) 129(97)  81(65)EOSH (1.0) 41 MeFBSE-MDI-HEA (6.0) 129(98)  82(67) EOSH (1.0) 42MeFBSE-MDI-HEA (8.3) 131(111) 81(67) EOSH (1.0) 43 MeFBSE-MDI-HEA (4.0)130(115) 80(69) DDSH (1.0) 44 MeFBSE-MDI-HEA (8.0) 128(115) 80(69) DDSH(1.0)

Example 45 Preparation of MeFBSE-MDI-HEA/methacryloxy PropylPolydimethyl Silicone, 80/20 Graft Copolymer

A 125 ml bottle was charged with 2.0 g MeFBSE-MDI-HEA, 0.5 gmethacryloxy propyl polydimethyl silicone (available from Shin EtsuChemical Co, Tokyo), 14.4 g ethyl acetate and 26 mg “Vazo 67”. Theresulting mixture was purged with nitrogen for two minutes, and thebottle was sealed and kept in a rotating water bath at 70° C. for 24hours. To the resulting cloudy solution was added 5.0 g DMF. Sizeexclusion chromatography (SEC) analysis showed 90.4% conversion withMn=13,200; Mw=28,800 and Mw/Mn=2.2.

Example 46 Preparation of MeFBSE-MDI-HEA/methacryloxy PropylPolydimethyl Silicone, 60/40 Graft Copolymer

A 125 ml bottle was charged with 1.51 g MeFBSE-MDI-HEA, 1.01 gmethacryloxy propyl polydimethyl silicone (available from Shin EtsuChemical Co., Tokyo), 14.4 g ethyl acetate and 22 mg “Vazo 67”. Theresulting mixture was purged with nitrogen for two minutes, and thebottle was sealed and kept in a rotating water bath at 70° C. for 24hours. To the resulting cloudy solution was added 5.0 g DMF. SECanalysis showed 85.4% conversion with Mn=14,400; Mw=36,300 andMw/Mn=2.5. TABLE 5 Examples 45-46 Contact Angle in degreesFluoroacrylate/Comonomer Advancing (Receding) Ex. Composition (molarratio) Water Hexadecane 45 MeFBSE-MDI-HEA (80) 118(99)  71(54)methacryloxy propyl polydimethyl silicone (20) 46 MeFBSE-MDI-HEA (60)127(107) 80(62) methacryloxy propyl polydimethyl silicone (40)

Example 47 Release Coatings

The copolymer of Example 27 was diluted to 5% solids with toluene. Thesolution was then coated with a #6 wire wound (Mayer) rod onto a 1.6 milprimed polyester terephthalate film. The coated film was attached to afiberboard frame and dried for 15 minutes at 65° C.

The test method used to evaluate the release coatings was a modificationof the industry standard peel adhesion test used to evaluate pressuresensitive adhesive coated materials. The standard test is described indetail in various publications of the American Society for Testing andMaterials (ASTM), Philadelphia, Pa., and the Pressure Sensitive TapeCouncil (PSTC), Glenview, Ill. The modified standard method is describedin detail below. The reference source of the standard test method isASTM D3330-78 PSTC-1 (11/75)

2.54 cm by 15.24 cm strips of Scotch® Performance Masking Tape 233+(available from 3M Company, St. Paul, Minn.) were rolled down onto thecoated polyester film with a 2.04 kg rubber roller. The laminatedsamples were then aged 1 week at 22° C. and 50% relative humidity or 16hours at 65° C. Prior to testing, the heat-aged samples wereequilibrated to 22° C. and 50% relative humidity for 24 hours.

Release testing was conducted by mounting the masking tape/coated filmlaminate to the stage of an Instrumentors, Inc. slip/peel tester (model3M90) with double coated tape. The force required to remove the maskingtape at 180 degrees and 228.6 cm/minute was then measured. Tapere-adhesions were also measured by adhering the freshly peeled maskingtape to a clean glass plate and measuring the peel adhesion in normalfashion using the same Instrumentors slip/peel tester indicated above,again peeling at 228.6 cm/min and at a 180 degree peel angle. Theresults of these peel tests are shown in Table 6.

Comparative Example 13 (C13) Release Coating ComprisingMeFOSEA/MMA/St/AA, 60/16/15/9

120 g MeFOSEA (C₈F₁₇SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂) was charged to a 2 literreaction flask equipped with a heating mantle, a condenser, N₂ inlet andan agitator. The flask was heated to 70° C. to melt MeFOSEA. Then apremix of 32 g methyl methacrylate, 30 g styrene, 18 g acrylic acid, 6.0g Rhodacal DS-10 surfactant, 5.71 g Zonyl™ FSP (DuPont) surfactant and600 g deionized water was charged to the flask. The resulting milkysolution was purged with N₂ for 5 minutes at liter per minute and heatedto 50° C. followed by addition of initiator, 0.3 g K₂SO₂O(potassiumpersulfate), dissolved in 10 g water. The reaction mixture was heated at50° C. for 1 hr. The temperature was raised to 75° C. and the reactionwas carried out for additional 5 hours. The resulting emulsion wascooled down to room temperature. The % solids were measured to be 26%,resulting in 99.5% conversion. Release coatings were prepared and testedas described in Example 45. The results are shown in Table 6 below.TABLE 6 Example 47 and Comparative Example C13 Example Example Example47 C13 Example 47 C13 Peel Force Peel Force Re- Re- from from adhesionadhesion Release Release Peel Force Peel Force Coating Coating fromGlass from Glass Sample (g/cm) (g/cm) (g/cm) (g/cm) 7 days @ 22° C.122.8 200.9 625.0 468.7 16 hrs @ 65° C. 267.8 401.8 502.2 390.6

Example 48

The copolymer of Example 45 was coated and tested according to themethods described in Example 47 with the exception that SCOTCH MAGICTAPE 810 (Available from 3M Company) was used in place of SCOTCHPERFORMANCE MASKING TAPE 233+. The results are shown in Table 7 belowTABLE 7 Peel Force from Readhesion Peel Release Coating Force from GlassExample 48 (g/cm) (g/cm)  7 days @ 22° C. 95.2 357.0 16 hrs @ 65° C.148.8 312.5

Example 49

Release coating of Example 47 was prepared and tested according to themethods described above using a silicone polyurea pressure sensitiveadhesive that was prepared and coated as described in U.S. Pat. No.6,569,521 (see Example 31). The peel force from the release coating andsubsequent readhesion to glass was measured. Three aging conditions wereevaluated: 7 days at 22° C. (50% relative humidity), 7 days at 50° C.and 3 days at 70° C. The results are shown in Table 8 below TABLE 8 PeelForce from Readhesion Peel Release Coating Force from Glass Example 49(g/cm) (g/cm) 7 days @ 22° C. 11.8 546.8 7 days @ 50° C. 18.1 580.3 3days @ 70° C. 27.2 580.3

Various modifications and alteration to this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention. It should be understood that thisinvention is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of theinvention intended to be limited only by the claims set forth herein asfollows.

1. A fluoroacrylate represented by the following general formula:C_(n)F_(2n+1)—X—OC(O)NH—A—HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂ wherein:n=1 to 5,

R=H or an alkyl group of 1 to 4 carbon atoms, m=2 to 8,R_(f)=C_(n)F_(2n+1), y=0 to 6, q=1 to 8, A=an unbranched symmetricalkylene group, arylene group, or aralkylene group, p=2 to 30, and R′=H,CH₃, or F.
 2. The fluoroacrylate of claim 1 wherein said n is 1 to
 4. 3.The fluoroacrylate of claim 2 wherein n is
 4. 4. The fluoroacrylate ofclaim 1 wherein said X is


5. The fluoroacrylate of claim 4 wherein said R is CH₃.
 6. Thefluoroacrylate of claim 5 wherein said m is 2 to
 4. 7. Thefluoroacrylate of claim 1 wherein said A is selected from the groupconsisting of —C₆H₁₂—,


8. The fluoroacrylate of claim 7 wherein said A is


9. The fluoroacrylate of claim 1 wherein said p is 2 to
 12. 10. Thefluoroacrylate of claim 9 wherein said p is selected from the groupconsisting of 2, 4, 6, 10, and
 12. 11. The fluoroacrylate of claim 10wherein said p is
 2. 12. The fluoroacrylate of claim 1 wherein said R′is H.
 13. A fluorinated isocyanate represented by the following generalformula:C_(n)F_(2n+1)—X—OC(O)NH—A—NCO wherein: n=1 to 5,

R=H or an alkyl group of 1 to 4 carbon atoms, m=2 to 8,R_(f)=C_(n)F_(2n+1), y=0 to 6, q=1 to 8, and A=an unbranched symmetricalkylene group, arylene group, or aralkylene group.
 14. A fluorinatedacrylic polymer comprising repeating units of the fluoroacrylate ofclaim
 1. 15. The fluorinated acrylic polymer of claim 14 furthercomprising repeating units derived from one or more nonfunctionalcomonomers.
 16. The fluorinated acrylic polymer of claim 14 furthercomprising repeating units derived from one or more functionalcomonomers.
 17. A coating composition comprising a solvent and thefluorinated acrylic polymer of claim
 14. 18. An article comprising asubstrate having one or more surfaces coated with the coatingcomposition of claim
 17. 19. The article of claim 18 wherein saidsubstrate is a hard substrate or a fibrous substrate.
 20. A releasecoating composition comprising a solvent and the fluorinated acrylicpolymer of claim
 14. 21. An article comprising a substrate having one ormore surfaces coated with the release coating composition of claim 20.